Free Radical-Initiated Reaction of Ethylene with Halomethanes

Harmon, John B.; Ford, T.A.; Hanford, W. E.; Joyce, Robert M.

doi:10.1021/ja01161a095

Cited by 45 publications

(8 citation statements)

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“…10 Benzoyl peroxide has been reported to catalyze the addition of methylene iodide to ethylene to give 1,3-diiodopropane. 11 The most unlikely step is 4, since radical displacements on carbon of this type are believed to be uncommon.…”

Section: Resultsmentioning

confidence: 99%

Photolysis of Methylene Iodide in the Presence of Olefins

Blomstrom¹,

Herbig²,

Simmons³

1965

J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Photolysis of Methylene Iodide in the Presence of Olefins

Blomstrom¹,

Herbig²,

Simmons³

1965

J. Org. Chem.

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“…Alcohol (ethanol) is added to reagent grade chloroform for this purpose (15). It is also possible that chloroform itself might stabilize the lipid system by reacting with free radical initiators or by acting as a chain terminator (16). None of these suggestions, however, explain the relatively low stability of the acetone extracted oils.…”

Section: Resultsmentioning

confidence: 99%

Effects of extraction, solvents, cold pressing, and period of storage upon oven stability of raw peanut oil

Brown

Cater

Mattil

1974

J Americ Oil Chem Soc

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Keeping time (oven stability, 60 C), oleate/linoleate ratios, peroxide values, and free fatty acid numbers were determined on oils from 5 peanut varieties grown at 2 Texas locations in 1972. Coldpressing within polyethylene bags (bag-pressing) resuited in increased oven stabilities and better correlations between oleate/tinoleate ratios and oven keeping times in comparison to cold-pressed oils. Average relative storage stabilities for the solvent extracted oils were: chloroform-methanol (3:1) >> cyclohexane ether > acetone -----bag-pressed > cold-pressed. Correlations of oleate/linoleate ratios and keeping times were increased using low peroxide ether in place of reagent grade ether. Extracted oils from samples including skins appeared to have longer keeping times than those minus skins. Oven keeping times and correlations with oleate/linoleate ratios decreased with extended peanut storage times (11 months), but the use of chloroform-methanol tended to compensate for this effect. For samples taken from storage after 3 and 6 months, the following average correlations were obtained: bag-pressed, 0.27; chloroform-methanol (without skins), 0.87; chloroformmethanol (with skins), 0.90; ether (reagent), 0.49; ether (low peroxide), 0.89; cyclohexane, 0.87; and acetone, 0.62. Generally poor correlations were found between oven stability and peroxide and free fatty acid numbers. Differences in the degree to which minor components are extracted from the cotyledons and skins, interacticn between the oils, and residual traces of solvents c,t trace impurities in solvents were suggested as possible factors leading to differences in keeping times of solvent extracted oils.

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“…This interpretation correlates with experimental C-H and C-Cl bond dissociation enthalpies ARTICLE for chloroform (H-CCl 3 , 95.2 kcal/mol vs. Cl-CHCl 2 , 79.2 kcal/mol) and for methylene chloride (H-CHCl 2 , 100.6 kcal/ mol vs. Cl-CH 2 Cl, 82.8 kcal/mol). 35 This interpretation is counter to assertions in the older literature 24,36 and calculation in the recent literature 37 that the C-H bond in CHCl 3 and CH 2 Cl 2 is the site of chain transfer in radical polymerizations. Contrary to the CHCl 3 and CH 2 Cl 2 behavior, t-butyl chloride displays a large chain transfer deuterium isotope effect [ Fig.…”

Section: Journal Of Polymer Sciencementioning

confidence: 94%

Polymerization of mono‐, Di‐, and trichloroethyl methacrylates: A study in chain transfer

Snow

2016

J. Polym. Sci. Part A: Polym. Chem.

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Bulk free radical polymerization of the monomer series CH 2 5 C(CH 3 )C(O)OCH 2 CH 3-n Cl n , n 5 1, 2, 3, yields an unexpectedly crosslinked product with a crosslink density that increases with decreasing chlorine content of the respective monomer (n 5 3 < n 5 2 < n 5 1). This chlorine substituent effect is investigated by correlation with chain transfer constant measurements for four homologous series of chloroalkyl compounds (chloroethyl acetates (CH 3 C(O)OCH 2 CH 3-n Cl n , n 5 1,2,3); chloromethanes (CH 4-n Cl n , n 5 2,3,4) and CD 2 Cl 2 and CDCl 3 analogs; butyl chloride isomers (n-, iso-, sec-, tert-) and tert-C 4 D 9 Cl analog; and nine chloroethanes (C 2 H n26 Cl n , n 5 1-6)) in a methyl methacrylate polymerization. The pattern conveyed by the magnitude of chain transfer constants and deuterium isotope effects is consistent with a vicinal chlorine effect (i.e., chlorine activation of a vicinal hydrogen for abstraction) to account for the relative activities of the four series of model compounds and for the propensity of the chloroethyl methacrylates to crosslink in a bulk free radical polymerization. The chloroalkyl moiety's contribution to chain transfer is relatively modest ( 10 24 ), but, when incorporated as a monomer pendant group in free radical polymerizations, it is effective in broadening molecular weight to the extent of resulting in a crosslinked polymer. Published 2016. † J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 93-106

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Free Radical-Initiated Reaction of Ethylene with Halomethanes

Cited by 45 publications

References 0 publications

Photolysis of Methylene Iodide in the Presence of Olefins

Photolysis of Methylene Iodide in the Presence of Olefins

Effects of extraction, solvents, cold pressing, and period of storage upon oven stability of raw peanut oil

Polymerization of mono‐, Di‐, and trichloroethyl methacrylates: A study in chain transfer

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